WO2014112151A1 - Alloy and method for producing same - Google Patents

Alloy and method for producing same Download PDF

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WO2014112151A1
WO2014112151A1 PCT/JP2013/073399 JP2013073399W WO2014112151A1 WO 2014112151 A1 WO2014112151 A1 WO 2014112151A1 JP 2013073399 W JP2013073399 W JP 2013073399W WO 2014112151 A1 WO2014112151 A1 WO 2014112151A1
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atomic
alloy
composition ratio
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samples
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PCT/JP2013/073399
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French (fr)
Japanese (ja)
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吉見享祐
丸山公一
後藤孝
宮本慎平
金子昂弘
森山貴裕
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国立大学法人東北大学
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Priority to JP2014557315A priority Critical patent/JP5876943B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/06—Casting non-ferrous metals with a high melting point, e.g. metallic carbides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon

Definitions

  • the present invention relates to an alloy and a manufacturing method thereof, for example, an alloy containing Mo, Si and B and a manufacturing method thereof.
  • Alloys used for high-pressure turbines and the like are required to be lightweight, high in strength and excellent in heat resistance.
  • an alloy there is a molybdenum alloy containing molybdenum (Mo).
  • Mo molybdenum
  • an alloy containing Mo, Si (silicon) and B (boron) for example, Patent Documents 1 and 2) and an MHC alloy containing hafnium (Hf) are known.
  • Non-patent Documents 1 and 2 the eutectic reaction temperature between Mo and Mo 5 SiB 2 is about 2060 ° C. to 2100 ° C.
  • Mo and TiC titanium carbide
  • Mo and ZrC zirconium carbide
  • Mo and ZrC zirconium carbide
  • Molybdenum alloy has a high melting point, and is formed by extruding powder sintered body. For this reason, in order to mold a complicated shape, cutting or the like is performed, and the manufacturing cost is increased. On the other hand, when a molded body is formed with powder sintering, problems such as a decrease in strength occur. On the other hand, expensive equipment is used to melt and cast the molybdenum alloy. Therefore, there is a demand for an alloy that is lightweight, has high strength, has excellent heat resistance, and can be melted at a relatively low temperature so that it can be easily manufactured by a casting method.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide an alloy that is lightweight, has high strength, has excellent heat resistance, and is soluble at a relatively low temperature.
  • the present invention is an alloy having Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N as main components.
  • ADVANTAGE OF THE INVENTION According to this invention, the alloy which is lightweight and high intensity
  • At least one element of Ti, Zr, and Hf may be Ti, and at least one element of C and N may be C.
  • the structure is a co-phase Mo 5 SiB 2 and TiC to.
  • the Mo composition ratio is 52 atomic% or more and 80 atomic% or less
  • the Si composition ratio is 1.5 atomic% or more and 25 atomic% or less
  • the B composition ratio is 3 atomic% or more and It is 25 atomic% or less
  • the composition ratio of Ti is 0.1 atomic% or more and 15 atomic% or less
  • the composition ratio of C is 0.1 atomic% or more and 15 atomic% or less. it can.
  • the Mo composition ratio is 60 atomic% or more and 75 atomic% or less
  • the Si composition ratio is 1.7 atomic% or more and 6.7 atomic% or less
  • the B composition ratio is 3.3 atomic%.
  • the composition ratio of Ti is 5.0 atomic% or more and 15.0 atomic% or less
  • the composition ratio of C is 5.0 atomic% or more and 15.0 atomic%. It can be set as the structure which is atomic% or less.
  • the composition ratio of Ti is 10 atomic% or more, and the composition ratio of C is 10 atomic% or less.
  • At least one element of Ti, Zr, and Hf may be Zr, and at least one element of C and N may be C.
  • the structure is a co-phase Mo 5 SiB 2 and ZrC to.
  • the present invention is to manufacture an alloy containing Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N by using a casting method.
  • An alloy production method characterized by the following. ADVANTAGE OF THE INVENTION According to this invention, the alloy which is lightweight and high intensity
  • At least one element of Ti, Zr, and Hf may be Ti, and at least one element of C and N may be C.
  • At least one element of Ti, Zr, and Hf may be Zr, and at least one element of C and N may be C.
  • FIG. 1 is a diagram showing a method for manufacturing an alloy in Examples and Comparative Examples.
  • FIG. 2A and FIG. 2B are observation photographs of the microstructures of samples A1 and A2, respectively.
  • FIGS. 3A and 3B are observation photographs of the microstructures of samples A3 and A4, respectively.
  • 4 (a) and 4 (b) are observation photographs of the microstructures of samples B1 and B2, respectively.
  • FIG. 5A and FIG. 5B are observation photographs of the microstructures of samples B3 and B4, respectively.
  • FIG. 6 is a diagram showing the measurement results of the stress-strain curve at 1400 ° C. for samples A1 to A4.
  • FIG. 7 is a diagram showing measurement results of stress-strain curves at 1400 ° C. for samples B1 to B4.
  • FIG. 1 is a diagram showing a method for manufacturing an alloy in Examples and Comparative Examples.
  • FIG. 2A and FIG. 2B are observation photographs of the microstructures of samples A1 and A2, respectively.
  • FIG. 8 is a diagram showing the measurement results of peak stress with respect to the temperature of samples A3 and B3.
  • FIG. 9 is a diagram showing the measurement results of Young's modulus with respect to the temperatures of samples A3 and B3.
  • FIG. 10 is a diagram showing the densities of samples A1 to A4 and B1 to B4.
  • FIG. 1 is a diagram showing a method for manufacturing an alloy in Examples and Comparative Examples. Referring to FIG. 1, each material is weighed (step S10). As materials, Mo, Si, B, TiC and Ti were used. The weighed material is melted using the arc melting method (step S12). An alloy is cast from the melted material (step S14).
  • Table 1 is a table showing the weight% (wt%) and atomic% (at%) of each element of the prepared sample.
  • No. Samples 2, 5, 9 and 14 correspond to samples A1 to A4, respectively.
  • Samples 4, 8, 13 and 16 correspond to samples B1 to B4, respectively.
  • No. 1 to No. 28, Si: B 1: 2 (atomic ratio).
  • No. 1 to No. 16, Ti: C 1: 1 (atomic ratio).
  • No. 17 to No. 28, Ti: C x (1 ⁇ x ⁇ 2): 1 (atomic ratio).
  • Table 2 is a table showing the density of each sample and the results of investigation on dissolution at 1800 ° C., 1900 ° C. and 2000 ° C.
  • Table 3 is a table showing the results of investigating the weight% (wt%), atomic% (at%), and dissolution at 1800 ° C., 1900 ° C., 2000 ° C. and 2100 ° C. of each element of a sample prepared as a comparative example. .
  • the density of all the measured samples of Examples is 9.01 g / cm 3 or less.
  • Sample No. All samples after 5 were dissolved at 2000 ° C. It can be seen that the melting point decreases when the Mo composition ratio is 60 atomic% or more and 75 atomic% or less. Moreover, it turns out that a density is small.
  • a sample to be dissolved tends to have a high composition ratio of Si and B and a small composition ratio of Ti and C.
  • the Si composition ratio is preferably 1.7 atomic percent or more, more preferably 3.3 atomic percent or more, and even more preferably 5.0 atomic percent or more.
  • the composition ratio of Si is preferably 6.7 atomic% or less.
  • the composition ratio of B is preferably 3.3 atomic% or more, more preferably 6.7 atomic% or more, and further preferably 10 atomic% or more.
  • the composition ratio of B is preferably 13.3 atomic% or less.
  • the composition ratio of Ti is preferably 15.0 atomic% or less, more preferably 13.3 atomic% or less, and further preferably 12.5 atomic% or less.
  • the composition ratio of Ti is preferably 5.0 atomic% or more.
  • the composition ratio of C is preferably 15.0 atomic% or less, more preferably 13.3 atomic% or less, and further preferably 12.5 atomic% or less.
  • the composition ratio of C is preferably 5.0 atomic% or more.
  • the composition ratio of Ti is made larger than the composition ratio of C.
  • the density becomes 8.6 g / cm 3 or less and can be dissolved at 2000 ° C.
  • the C composition ratio is 10 atomic% or less and the Ti composition ratio is 10 atomic% or more.
  • FIGS. 2A to 3B are observation photographs of the microstructures of samples A1 to A4, respectively. The fine structure was observed using SEM (scanning electron microscope). Mo ss is a solid solution phase of Mo, T 2 is a phase of Mo 5 SiB 2 , Mo 2 C is a phase of Mo 2 C, and TiC is a phase of TiC. As shown in FIGS. 2A to 3B, samples A1 to A4 are found to be a co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and TiC.
  • FIGS. 4A to 5B are observation photographs of the microstructures of samples B1 to B4, respectively. Similar to FIGS. 2A to 3B, the microstructure was observed using a SEM (scanning electron microscope). As shown in FIGS. 4 (a) to 5 (b), the samples B1 to B4, like the samples A1 to B4, are a co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and TiC. Recognize.
  • FIG. 6 is a diagram showing the measurement results of the stress-strain curve at 1400 ° C. for samples A1 to A4. For comparison, a stress-strain curve of an MHC alloy is shown. Referring to FIG. 6, the yield strength of each sample was more than twice that of the MHC alloy. In particular, a sample having a small composition ratio of TiC and a high composition ratio of SiB 2 has a high yield strength. Thus, it can be seen that Samples A1 to A4 have high strength at high temperatures.
  • FIG. 7 is a diagram showing measurement results of stress-strain curves at 1400 ° C. for samples B1 to B4. For comparison, a stress-strain curve of an MHC alloy is shown. Referring to FIG. 7, the yield strength of each sample was higher than that of the MHC alloy. In particular, a sample having a small composition ratio of TiC and a high composition ratio of SiB 2 has a high yield strength. Thus, it can be seen that the samples B1 to B4 are high in strength at high temperatures, similar to the samples A1 to A4.
  • FIG. 8 is a diagram showing the measurement results of peak stress with respect to the temperature of samples A3 and B3.
  • the peak stress ⁇ indicates the peak value of the stress ⁇ in the stress-strain curve.
  • the peak stresses of MHC (molybdenum / hafnium carbide) alloy, TZM (titanium / zirconium / molybdenum) alloy, and Mo0.6-Si7.9-B are shown.
  • the white circle is B3, the white square is A3, the black circle is the MHC alloy, and the black square is the measurement point of the TZM alloy.
  • the slanted white square is the value described in the literature of Mo-6.1Si-7.9B.
  • the curve is an approximate curve.
  • Sample B3 has a higher peak stress at any temperature than Mo-6.1Si-7.9B, MHC alloy and TZM alloy known as heat-resistant alloys. At 1000 ° C., the peak stress is 1800 MPa, which is very large compared to MHC alloy, TZM alloy, and Mo-6.1Si-7.9B alloy. Moreover, at 1600 degreeC, it has a peak stress of about 400 MPa. Sample A3 has a peak stress comparable to that of sample B3 at 1400 ° C. The sample A3 is considered to have a peak stress comparable to that of the sample B3 at other temperatures. In addition, it is considered that the peak stress at a high temperature is large in the other samples as well as the sample B3. As described above, an alloy containing Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N as a main component is at a high temperature of 1000 ° C. or more. Excellent high strength.
  • FIG. 9 is a diagram showing the measurement results of Young's modulus with respect to the temperatures of samples A3 and B3. For comparison, the Young's modulus of W (tungsten), Mo, Mo-2Si alloy and Mo-3Si alloy is shown. Referring to FIG. 9, each sample has a higher Young's modulus from room temperature to 1000 ° C. than Mo and Mo—Si alloy. Thus, it can be seen that Samples A3 and B3 have high rigidity at high temperatures.
  • FIG. 10 is a diagram showing the densities of samples A1 to A4 and B1 to B4. For comparison, the densities of pure Ni (nickel), Rene′N5 alloy, TMS-138 alloy, Mo 5 SiB 2 and pure Mo are shown. Referring to FIG. 6, the density of samples A1 to A4 and B1 to B4 is 8.7 g / cm 3 to 9.01 g / cm 3 . Samples A1 to A4 and B1 to B4 have a density lower than that of pure Mo, and the same density as that of Ni 'alloys Rene′N5 alloy, TMS-138 alloy, and Mo 5 SiB 2 .
  • Ni, ReneN5 alloy and TMS-138 alloy are small in density and lightweight, but have a melting point of about 1400 ° C. and cannot be used as a high heat-resistant alloy used at about 1500 ° C.
  • Mo 5 SiB 2 is lightweight and highly heat resistant, but has a melting point of about 2200 ° C. and is difficult to manufacture by a casting method.
  • the alloys according to the examples are mainly composed of Mo, Si, B, Ti and C. Thereby, as shown in Table 3, it can melt
  • the composition ratio of Mo is 52 atomic% or more and 80 atomic% or less
  • the composition ratio of Si is 1.5 atomic% or more and 25 atomic% or less
  • the composition ratio of B is 3 atomic% or more and 25 atomic% or less.
  • the composition ratio of Ti is preferably 0.1 atomic% or more and 15 atomic% or less
  • the composition ratio of C is preferably 0.1 atomic% or more and 15 atomic% or less.
  • the Mo composition ratio is preferably 80 atomic% or less in order to lower the melting point. In order to increase the strength, the Mo composition ratio is preferably 52 atomic% or more. Since it is based on the Mo—Si—B ternary system, the composition ratio of Si is 1.5 atomic% or more and 25 atomic% or less, and the composition ratio of B is 3 atomic% or more and 25 atomic% or less. Is preferred. Ti and C are preferably 0.1 atomic percent or more for lowering the melting point.
  • these alloys have a low melting point, high strength and high strength due to the co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and TiC. Light weight can be realized.
  • the melting temperature is set to 2100 ° C. or lower, so that the Mo composition ratio is 65 atomic% or more and the B composition ratio is 20 It is preferably at most atomic%. Further, the Mo composition ratio is preferably 75 atomic% or less.
  • the composition ratio of B is preferably 10 atomic% or more. In order to set the melting temperature to 2000 ° C. or less, it is preferable that the Mo composition ratio is 67 atomic% or more and the B composition ratio is 15 atomic% or less.
  • the composition ratio of Mo is preferably 73 atomic percent or less.
  • the composition ratio of B is preferably 10 atomic% or more.
  • the density is 9.1 g / cm 3 or more. Therefore, it is difficult to reduce the weight of the alloy.
  • the density of the alloy can be about 8.8 g / cm 3 .
  • the melting temperature increases. In the examples, the density can be reduced to about 9.0 g / cm 3 or less, and the melting temperature can be lowered. Therefore, it can be melted at a relatively low temperature and the alloy can be easily reduced in weight.
  • Zr and Hf have the same period as Ti in the periodic table, and the properties are similar to Ti.
  • the affinity with C or N is large. Therefore, Zr and Hf can be used instead of Ti.
  • Ti is preferable for weight reduction.
  • N shows the same behavior as C when alloyed, N can be used instead of C. Therefore, the alloy may be composed mainly of Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N.
  • the alloy can be mainly composed of Mo, Si, B, Zr and C. Further, the alloy can contain Mo, Si, B, Ti, Zr and C as main components. In this case, since the alloy is a co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and ZrC, the melting point is low, and high strength and light weight can be realized.
  • Mo, Si, B, TiC, TiN, Ti, Zr, or the like can be used as appropriate.
  • a material melting method in step S12 a plasma melting method or the like can be used in addition to the arc melting method.
  • An alloy mainly composed of Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N is dissolved at a temperature of about 2000 ° C. It can be manufactured using inexpensive equipment. Further, a product having a complicated shape and / or a large product can be easily manufactured. Further, the strength can be increased at a temperature of 1000 ° C. or higher, and the weight can be reduced. For this reason, this alloy can be applied to a high-pressure turbine blade of a jet engine or a gas turbine as a heat-resistant alloy. Moreover, it can be applied to various processing tools and special molds in place of WC (tungsten carbide). Furthermore, it can be used for a high-temperature and high-pressure vessel.
  • WC tungsten carbide

Abstract

The present invention relates to an alloy that is mainly composed of Mo, Si, B, Ti, at least one of Zr and Hf, and at least one of C and N. The present invention also relates to a method for producing an alloy that is mainly composed of Mo, Si, B, Ti, at least one of Zr and Hf, and at least one of C and N by a casting process.

Description

合金およびその製造方法Alloy and production method thereof
　本発明は合金およびその製造方法に関し、例えばＭｏ、ＳｉおよびＢを含む合金およびその製造方法に関する。 The present invention relates to an alloy and a manufacturing method thereof, for example, an alloy containing Mo, Si and B and a manufacturing method thereof.
　高圧タービン等に用いられる合金は、軽量かつ高強度であり耐熱性に優れることが求められる。このような合金としてモリブデン（Ｍｏ）を含むモリブデン合金がある。例えば、Ｍｏ、Ｓｉ（シリコン）およびＢ（ホウ素）を含む合金（例えば特許文献１および２）やハフニウム（Ｈｆ）を含むＭＨＣ合金が知られている。 Alloys used for high-pressure turbines and the like are required to be lightweight, high in strength and excellent in heat resistance. As such an alloy, there is a molybdenum alloy containing molybdenum (Mo). For example, an alloy containing Mo, Si (silicon) and B (boron) (for example, Patent Documents 1 and 2) and an MHC alloy containing hafnium (Hf) are known.
　ＭｏとＭｏ５ＳｉＢ２との共晶反応温度は、２０６０℃から２１００℃程度であることが知られている（非特許文献１および２）。一方、ＭｏとＴｉＣ（炭化チタン）とは共晶反応することが知られている。ＭｏとＴｉＣとの共晶温度は約２１７５℃であることが知られている（非特許文献３）。また、ＭｏとＺｒＣ（炭化ジルコニウム）とは共晶反応することが知られている。ＭｏとＺｒＣとの共晶温度は約２５００℃であることが知られている（非特許文献３）。 It is known that the eutectic reaction temperature between Mo and Mo 5 SiB 2 is about 2060 ° C. to 2100 ° C. (Non-patent Documents 1 and 2). On the other hand, it is known that Mo and TiC (titanium carbide) undergo a eutectic reaction. It is known that the eutectic temperature of Mo and TiC is about 2175 ° C. (Non-patent Document 3). Mo and ZrC (zirconium carbide) are known to undergo a eutectic reaction. It is known that the eutectic temperature of Mo and ZrC is about 2500 ° C. (Non-patent Document 3).
特開２００４－１１５８３３号公報JP 2004-115833 A 特開２００８－１１４２５８号公報JP 2008-114258 A
　モリブデン合金は融点が高いため、粉末焼結体を押出加工等して成型される。このため、複雑な形状を成型するためには、切削加工等を行なうことになり、製造コストが高くなる。逆に、粉末焼結のままで成形体とした場合には、強度の低下等の問題が発生する。一方、モリブデン合金を溶解し鋳造するためには、高額な設備を用いることになる。そこで、鋳造法により簡単に製造可能とするため、軽量かつ高強度であり耐熱性に優れ、かつ比較的低温において溶解可能な合金が求められている。 Molybdenum alloy has a high melting point, and is formed by extruding powder sintered body. For this reason, in order to mold a complicated shape, cutting or the like is performed, and the manufacturing cost is increased. On the other hand, when a molded body is formed with powder sintering, problems such as a decrease in strength occur. On the other hand, expensive equipment is used to melt and cast the molybdenum alloy. Therefore, there is a demand for an alloy that is lightweight, has high strength, has excellent heat resistance, and can be melted at a relatively low temperature so that it can be easily manufactured by a casting method.
　本発明は、上記課題に鑑みなされたものであり、軽量かつ高強度であり耐熱性に優れ、かつ比較的低温において溶解可能な合金を提供することを目的とする。 The present invention has been made in view of the above problems, and an object of the present invention is to provide an alloy that is lightweight, has high strength, has excellent heat resistance, and is soluble at a relatively low temperature.
　本発明は、Ｍｏと、Ｓｉと、Ｂと、Ｔｉと、ＺｒおよびＨｆの少なくとも１つの元素と、ＣおよびＮの少なくとも１つの元素と、を主成分とすることを特徴とする合金である。本発明によれば、軽量かつ高強度であり耐熱性に優れ、かつ比較的低温において溶解可能な合金を提供することができる。 The present invention is an alloy having Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N as main components. ADVANTAGE OF THE INVENTION According to this invention, the alloy which is lightweight and high intensity | strength, is excellent in heat resistance, and can melt | dissolve in a comparatively low temperature can be provided.
　上記構成において、鋳造された構成とすることができる。 In the above configuration, it may be a cast configuration.
　上記構成において、前記Ｔｉ、ＺｒおよびＨｆの少なくとも１つの元素はＴｉであり、前記ＣおよびＮの少なくとも１つの元素はＣである構成とすることができる。 In the above configuration, at least one element of Ti, Zr, and Hf may be Ti, and at least one element of C and N may be C.
　上記構成において、Ｍｏ固溶体相、Ｍｏ２Ｃ、Ｍｏ５ＳｉＢ２およびＴｉＣの共相である構成とすることができる。 In the above structure, it is possible to Mo solid solution phase, Mo 2 C, the structure is a co-phase Mo 5 SiB 2 and TiC to.
　上記構成において、Ｍｏの組成比は５２原子％以上かつ８０原子％以下であり、Ｓｉの組成比は１．５原子％以上かつ２５原子％以下であり、Ｂの組成比は３原子％以上かつ２５原子％以下であり、Ｔｉの組成比は０．１原子％以上かつ１５原子％以下であり、Ｃの組成比は、０．１原子％以上かつ１５原子％以下である構成とすることができる。 In the above configuration, the Mo composition ratio is 52 atomic% or more and 80 atomic% or less, the Si composition ratio is 1.5 atomic% or more and 25 atomic% or less, and the B composition ratio is 3 atomic% or more and It is 25 atomic% or less, the composition ratio of Ti is 0.1 atomic% or more and 15 atomic% or less, and the composition ratio of C is 0.1 atomic% or more and 15 atomic% or less. it can.
　上記構成において、Ｍｏの組成比は６０原子％以上かつ７５原子％以下であり、Ｓｉの組成比は１．７原子％以上かつ６．７原子％以下であり、Ｂの組成比は３．３原子％以上かつ１３．３原子％以下であり、Ｔｉの組成比は５．０原子％以上かつ１５．０原子％以下であり、Ｃの組成比は、５．０原子％以上かつ１５．０原子％以下である構成とすることができる。 In the above configuration, the Mo composition ratio is 60 atomic% or more and 75 atomic% or less, the Si composition ratio is 1.7 atomic% or more and 6.7 atomic% or less, and the B composition ratio is 3.3 atomic%. The composition ratio of Ti is 5.0 atomic% or more and 15.0 atomic% or less, and the composition ratio of C is 5.0 atomic% or more and 15.0 atomic%. It can be set as the structure which is atomic% or less.
　上記構成において、Ｔｉの組成比は１０原子％以上であり、かつＣの組成比は１０原子％以下である構成とすることができる。 In the above configuration, the composition ratio of Ti is 10 atomic% or more, and the composition ratio of C is 10 atomic% or less.
　上記構成において、前記Ｔｉ、ＺｒおよびＨｆの少なくとも１つの元素はＺｒであり、前記ＣおよびＮの少なくとも１つの元素はＣである構成とすることができる。 In the above configuration, at least one element of Ti, Zr, and Hf may be Zr, and at least one element of C and N may be C.
　上記構成において、Ｍｏ固溶体相、Ｍｏ２Ｃ、Ｍｏ５ＳｉＢ２およびＺｒＣの共相である構成とすることができる。 In the above structure, it is possible to Mo solid solution phase, Mo 2 C, the structure is a co-phase Mo 5 SiB 2 and ZrC to.
　本発明は、Ｍｏと、Ｓｉと、Ｂと、Ｔｉと、ＺｒおよびＨｆの少なくとも１つの元素と、ＣおよびＮの少なくとも１つの元素と、を主成分とする合金を鋳造法を用い製造することを特徴とする合金の製造方法である。本発明によれば、軽量かつ高強度であり耐熱性に優れ、かつ比較的低温において溶解可能な合金を提供することができる。 The present invention is to manufacture an alloy containing Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N by using a casting method. An alloy production method characterized by the following. ADVANTAGE OF THE INVENTION According to this invention, the alloy which is lightweight and high intensity | strength, is excellent in heat resistance, and can melt | dissolve in a comparatively low temperature can be provided.
　上記構成において、前記Ｔｉ、ＺｒおよびＨｆの少なくとも１つの元素はＴｉであり、前記ＣおよびＮの少なくとも１つの元素はＣである構成とすることができる。 In the above configuration, at least one element of Ti, Zr, and Hf may be Ti, and at least one element of C and N may be C.
　上記構成において、前記Ｔｉ、ＺｒおよびＨｆの少なくとも１つの元素はＺｒであり、前記ＣおよびＮの少なくとも１つの元素はＣである構成とすることができる。 In the above configuration, at least one element of Ti, Zr, and Hf may be Zr, and at least one element of C and N may be C.
　本発明によれば、軽量かつ高強度であり耐熱性に優れ、かつ比較的低温において溶解可能な合金を提供することができる。 According to the present invention, it is possible to provide an alloy that is light and high in strength, excellent in heat resistance, and soluble at a relatively low temperature.
図１は、実施例および比較例における合金の製造方法を示す図である。FIG. 1 is a diagram showing a method for manufacturing an alloy in Examples and Comparative Examples. 図２（ａ）および図２（ｂ）は、それぞれ試料Ａ１およびＡ２の微細組織の観察写真である。FIG. 2A and FIG. 2B are observation photographs of the microstructures of samples A1 and A2, respectively. 図３（ａ）および図３（ｂ）は、それぞれ試料Ａ３およびＡ４の微細組織の観察写真である。FIGS. 3A and 3B are observation photographs of the microstructures of samples A3 and A4, respectively. 図４（ａ）および図４（ｂ）は、それぞれ試料Ｂ１およびＢ２の微細組織の観察写真である。4 (a) and 4 (b) are observation photographs of the microstructures of samples B1 and B2, respectively. 図５（ａ）および図５（ｂ）は、それぞれ試料Ｂ３およびＢ４の微細組織の観察写真である。FIG. 5A and FIG. 5B are observation photographs of the microstructures of samples B3 and B4, respectively. 図６は、試料Ａ１～Ａ４の１４００℃における応力－歪み曲線の測定結果を示す図である。FIG. 6 is a diagram showing the measurement results of the stress-strain curve at 1400 ° C. for samples A1 to A4. 図７は、試料Ｂ１～Ｂ４の１４００℃における応力－歪み曲線の測定結果を示す図である。FIG. 7 is a diagram showing measurement results of stress-strain curves at 1400 ° C. for samples B1 to B4. 図８は、試料Ａ３およびＢ３の温度に対するピーク応力の測定結果を示す図である。FIG. 8 is a diagram showing the measurement results of peak stress with respect to the temperature of samples A3 and B3. 図９は、試料Ａ３およびＢ３の温度に対するヤング率の測定結果を示す図である。FIG. 9 is a diagram showing the measurement results of Young's modulus with respect to the temperatures of samples A3 and B3. 図１０は、試料Ａ１～Ａ４およびＢ１～Ｂ４の密度を示す図である。FIG. 10 is a diagram showing the densities of samples A1 to A4 and B1 to B4.
　本発明者らは、Ｍｏと、Ｓｉと、Ｂと、Ｔｉ（チタン）、Ｚｒ（シルコニウム）およびＨｆ（ハフニウム）の少なくとも１つの元素と、Ｃ（炭素）およびＮ（窒素）の少なくとも１つの元素と、を主成分とすることにより、軽量かつ高強度であり耐熱性に優れ、かつ比較的低温において溶解可能な合金を製造可能であることを見出した。以下、本発明の実施例について説明する。 We have at least one element of Mo, Si, B, Ti (titanium), Zr (silconium) and Hf (hafnium), and at least one element of C (carbon) and N (nitrogen). As a main component, the inventors have found that it is possible to produce an alloy that is lightweight, has high strength, has excellent heat resistance, and is soluble at a relatively low temperature. Examples of the present invention will be described below.
　Ｍｏ、Ｓｉ、Ｂ、ＴｉおよびＣを主成分とする試料を作製した。比較例として、Ｍｏ、ＳｉおよびＢを主成分とする試料を作製した。図１は、実施例および比較例における合金の製造方法を示す図である。図１を参照し、各材料を秤量する（ステップＳ１０）。材料としては、Ｍｏ、Ｓｉ、Ｂ、ＴｉＣおよびＴｉを用いた。アーク溶解法を用い秤量した材料を溶解させる（ステップＳ１２）。溶解した材料により合金を鋳造する（ステップＳ１４）。 A sample mainly composed of Mo, Si, B, Ti and C was prepared. As a comparative example, a sample mainly composed of Mo, Si and B was prepared. FIG. 1 is a diagram showing a method for manufacturing an alloy in Examples and Comparative Examples. Referring to FIG. 1, each material is weighed (step S10). As materials, Mo, Si, B, TiC and Ti were used. The weighed material is melted using the arc melting method (step S12). An alloy is cast from the melted material (step S14).
　表１は、作製した試料の各元素の重量％（ｗｔ％）および原子％（ａｔ％）を示す表である。
Figure JPOXMLDOC01-appb-T000001
 Table 1 is a table showing the weight% (wt%) and atomic% (at%) of each element of the prepared sample.
Figure JPOXMLDOC01-appb-T000001
　Ｎｏ．２、５、９および１４の試料が、それぞれ試料Ａ１からＡ４に対応し、Ｎｏ．４、８、１３および１６の試料が、それぞれ試料Ｂ１からＢ４に対応する。Ｎｏ．１からＮｏ．２８において、Ｓｉ：Ｂ＝１：２（原子比）である。Ｎｏ．１からＮｏ．１６において、Ｔｉ：Ｃ＝１：１（原子比）である。Ｎｏ．１７からＮｏ．２８において、Ｔｉ：Ｃ＝ｘ（１＜ｘ≦２）：１（原子比）である。 No. Samples 2, 5, 9 and 14 correspond to samples A1 to A4, respectively. Samples 4, 8, 13 and 16 correspond to samples B1 to B4, respectively. No. 1 to No. 28, Si: B = 1: 2 (atomic ratio). No. 1 to No. 16, Ti: C = 1: 1 (atomic ratio). No. 17 to No. 28, Ti: C = x (1 <x ≦ 2): 1 (atomic ratio).
　表２は、各試料の密度および、１８００℃、１９００℃および２０００℃における溶解を調査した結果を示す表である。
Figure JPOXMLDOC01-appb-T000002
 Table 2 is a table showing the density of each sample and the results of investigation on dissolution at 1800 ° C., 1900 ° C. and 2000 ° C.
Figure JPOXMLDOC01-appb-T000002
　表３は、比較例として作製した試料の各元素の重量％（ｗｔ％）、原子％（ａｔ％）および１８００℃、１９００℃、２０００℃および２１００℃における溶解を調査した結果を示す表である。
Figure JPOXMLDOC01-appb-T000003
 Table 3 is a table showing the results of investigating the weight% (wt%), atomic% (at%), and dissolution at 1800 ° C., 1900 ° C., 2000 ° C. and 2100 ° C. of each element of a sample prepared as a comparative example. .
Figure JPOXMLDOC01-appb-T000003
　表２および表３において、「－」は調査していないことを示す。「溶解」の項において、「○」は全て溶解したことを示す。「△」は部分的に溶解したことを示す。「×」は溶解しないことを示す。 In Tables 2 and 3, “-” indicates that no investigation was conducted. In the “dissolved” section, “◯” indicates that all were dissolved. “Δ” indicates partial dissolution. “X” indicates that it does not dissolve.
　表１および表２のように、測定した全ての実施例の試料において、密度は９．０１ｇ／ｃｍ３以下である。試料Ｎｏ．５以降の試料は、全て２０００℃において溶解した。Ｍｏの組成比が６０原子％以上かつ７５原子％以下において、融点が低下することがわかる。また、密度が小さいことがわかる。溶解する試料は、ＳｉおよびＢの組成比が高く、ＴｉおよびＣの組成比が小さい傾向にある。Ｓｉの組成比は、１．７原子％以上が好ましく、３．３原子％以上がより好ましく、５．０原子％以上がさらに好ましい。Ｓｉの組成比は、６．７原子％以下が好ましい。Ｂの組成比は、３．３原子％以上が好ましく、６．７原子％以上がより好ましく、１０原子％以上がさらに好ましい。Ｂの組成比は、１３．３原子％以下が好ましい。Ｔｉの組成比は、１５．０原子％以下が好ましく、１３．３原子％以下がより好ましく、１２．５原子％以下がさらに好ましい。Ｔｉの組成比は、５．０原子％以上が好ましい。Ｃの組成比は、１５．０原子％以下が好ましく、１３．３原子％以下がより好ましく、１２．５原子％以下がさらに好ましい。Ｃの組成比は、５．０原子％以上が好ましい。 As shown in Tables 1 and 2, the density of all the measured samples of Examples is 9.01 g / cm 3 or less. Sample No. All samples after 5 were dissolved at 2000 ° C. It can be seen that the melting point decreases when the Mo composition ratio is 60 atomic% or more and 75 atomic% or less. Moreover, it turns out that a density is small. A sample to be dissolved tends to have a high composition ratio of Si and B and a small composition ratio of Ti and C. The Si composition ratio is preferably 1.7 atomic percent or more, more preferably 3.3 atomic percent or more, and even more preferably 5.0 atomic percent or more. The composition ratio of Si is preferably 6.7 atomic% or less. The composition ratio of B is preferably 3.3 atomic% or more, more preferably 6.7 atomic% or more, and further preferably 10 atomic% or more. The composition ratio of B is preferably 13.3 atomic% or less. The composition ratio of Ti is preferably 15.0 atomic% or less, more preferably 13.3 atomic% or less, and further preferably 12.5 atomic% or less. The composition ratio of Ti is preferably 5.0 atomic% or more. The composition ratio of C is preferably 15.0 atomic% or less, more preferably 13.3 atomic% or less, and further preferably 12.5 atomic% or less. The composition ratio of C is preferably 5.0 atomic% or more.
　Ｎｏ．１７からＮｏ．２８においては、Ｔｉの組成比をＣの組成比より大きくする。例えば、１＜Ｔｉの組成比／Ｃの組成比≦２である。これにより、密度が８．６ｇ／ｃｍ３以下となり、かつ２０００℃において溶解できる。例えば、Ｃの組成比を１０原子％以下とし、かつＴｉの組成比を１０原子％以上とすることが好ましい。 No. 17 to No. In 28, the composition ratio of Ti is made larger than the composition ratio of C. For example, 1 <Ti composition ratio / C composition ratio ≦ 2. Thereby, the density becomes 8.6 g / cm 3 or less and can be dissolved at 2000 ° C. For example, it is preferable that the C composition ratio is 10 atomic% or less and the Ti composition ratio is 10 atomic% or more.
　図２（ａ）から図３（ｂ）は、それぞれ試料Ａ１～Ａ４の微細組織の観察写真である。微細組織はＳＥＭ（走査型電子顕微鏡）を用いて観察した。ＭｏｓｓはＭｏの固溶体相、Ｔ２は、Ｍｏ５ＳｉＢ２の相、Ｍｏ２ＣはＭｏ２Ｃの相、ＴｉＣはＴｉＣの相を示している。図２（ａ）から図３（ｂ）のように、試料Ａ１～Ａ４は、Ｍｏ固溶体相、Ｍｏ２Ｃ、Ｍｏ５ＳｉＢ２およびＴｉＣの共相であることがわかる。 FIGS. 2A to 3B are observation photographs of the microstructures of samples A1 to A4, respectively. The fine structure was observed using SEM (scanning electron microscope). Mo ss is a solid solution phase of Mo, T 2 is a phase of Mo 5 SiB 2 , Mo 2 C is a phase of Mo 2 C, and TiC is a phase of TiC. As shown in FIGS. 2A to 3B, samples A1 to A4 are found to be a co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and TiC.
　図４（ａ）から図５（ｂ）は、それぞれ試料Ｂ１～Ｂ４の微細組織の観察写真である。図２（ａ）から図３（ｂ）と同様に、微細組織をＳＥＭ（走査型電子顕微鏡）を用いて観察した。図４（ａ）から図５（ｂ）のように、試料Ｂ１～Ｂ４は、試料Ａ１～Ｂ４と同様に、Ｍｏ固溶体相、Ｍｏ２Ｃ、Ｍｏ５ＳｉＢ２およびＴｉＣの共相であることがわかる。 FIGS. 4A to 5B are observation photographs of the microstructures of samples B1 to B4, respectively. Similar to FIGS. 2A to 3B, the microstructure was observed using a SEM (scanning electron microscope). As shown in FIGS. 4 (a) to 5 (b), the samples B1 to B4, like the samples A1 to B4, are a co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and TiC. Recognize.
　図６は、試料Ａ１～Ａ４の１４００℃における応力－歪み曲線の測定結果を示す図である。比較のためＭＨＣ合金の応力－歪み曲線を示す。図６を参照し、いずれの試料もＭＨＣ合金に比べ降伏強度が２倍以上となった。特に、ＴｉＣの組成比が小さく、ＳｉＢ２の組成比が高い試料は降伏強度が高くなる。このように、試料Ａ１～Ａ４は、高温において高強度であることがわかる。 FIG. 6 is a diagram showing the measurement results of the stress-strain curve at 1400 ° C. for samples A1 to A4. For comparison, a stress-strain curve of an MHC alloy is shown. Referring to FIG. 6, the yield strength of each sample was more than twice that of the MHC alloy. In particular, a sample having a small composition ratio of TiC and a high composition ratio of SiB 2 has a high yield strength. Thus, it can be seen that Samples A1 to A4 have high strength at high temperatures.
　図７は、試料Ｂ１～Ｂ４の１４００℃における応力－歪み曲線の測定結果を示す図である。比較のためＭＨＣ合金の応力－歪み曲線を示す。図７を参照し、いずれの試料もＭＨＣ合金に比べ降伏強度が大きくなった。特に、ＴｉＣの組成比が小さく、ＳｉＢ２の組成比が高い試料は降伏強度が高くなる。このように、試料Ｂ１～Ｂ４は、試料Ａ１～Ａ４と同様に、高温において高強度であることがわかる。 FIG. 7 is a diagram showing measurement results of stress-strain curves at 1400 ° C. for samples B1 to B4. For comparison, a stress-strain curve of an MHC alloy is shown. Referring to FIG. 7, the yield strength of each sample was higher than that of the MHC alloy. In particular, a sample having a small composition ratio of TiC and a high composition ratio of SiB 2 has a high yield strength. Thus, it can be seen that the samples B1 to B4 are high in strength at high temperatures, similar to the samples A1 to A4.
　図８は、試料Ａ３およびＢ３の温度に対するピーク応力の測定結果を示す図である。ピーク応力σは、応力－歪み曲線における応力σのピーク値を示している。比較のため、ＭＨＣ（モリブデン・ハフニウムカーバイド）合金、ＴＺＭ（チタン・ジルコニウム・モリブデン）合金、Ｍｏ０．６－Ｓｉ７．９－Ｂのピーク応力を示す。白丸がＢ３、白四角がＡ３、黒丸がＭＨＣ合金、および黒四角がＴＺＭ合金の測定点である。斜め白四角がＭｏ－６．１Ｓｉ－７．９Ｂの文献に記載された値である。曲線は近似曲線である。 FIG. 8 is a diagram showing the measurement results of peak stress with respect to the temperature of samples A3 and B3. The peak stress σ indicates the peak value of the stress σ in the stress-strain curve. For comparison, the peak stresses of MHC (molybdenum / hafnium carbide) alloy, TZM (titanium / zirconium / molybdenum) alloy, and Mo0.6-Si7.9-B are shown. The white circle is B3, the white square is A3, the black circle is the MHC alloy, and the black square is the measurement point of the TZM alloy. The slanted white square is the value described in the literature of Mo-6.1Si-7.9B. The curve is an approximate curve.
　試料Ｂ３は、Ｍｏ－６．１Ｓｉ－７．９Ｂ、耐熱合金として知られているＭＨＣ合金およびＴＺＭ合金と比較し、いずれの温度においてもピーク応力が大きい。１０００℃において、ピーク応力は１８００ＭＰａとＭＨＣ合金、ＴＺＭ合金、Ｍｏ－６．１Ｓｉ－７．９Ｂ合金に比べ非常に大きい。また、１６００℃において、約４００ＭＰａのピーク応力を有する。試料Ａ３は、１４００℃において試料Ｂ３と同程度のピーク応力を有する。試料Ａ３は、他の温度においても試料Ｂ３と同程度のピーク応力を有すると考えられる。また、他の試料においても試料Ｂ３と同様に高温でのピーク応力が大きいと考えられる。このように、Ｍｏと、Ｓｉと、Ｂと、Ｔｉと、ＺｒおよびＨｆの少なくとも１つの元素と、ＣおよびＮの少なくとも１つの元素と、を主成分とする合金は、１０００℃以上の高温において高強度性に優れている。 Sample B3 has a higher peak stress at any temperature than Mo-6.1Si-7.9B, MHC alloy and TZM alloy known as heat-resistant alloys. At 1000 ° C., the peak stress is 1800 MPa, which is very large compared to MHC alloy, TZM alloy, and Mo-6.1Si-7.9B alloy. Moreover, at 1600 degreeC, it has a peak stress of about 400 MPa. Sample A3 has a peak stress comparable to that of sample B3 at 1400 ° C. The sample A3 is considered to have a peak stress comparable to that of the sample B3 at other temperatures. In addition, it is considered that the peak stress at a high temperature is large in the other samples as well as the sample B3. As described above, an alloy containing Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N as a main component is at a high temperature of 1000 ° C. or more. Excellent high strength.
　図９は、試料Ａ３およびＢ３の温度に対するヤング率の測定結果を示す図である。比較のためＷ（タングステン）、Ｍｏ、Ｍｏ－２Ｓｉ合金およびＭｏ－３Ｓｉ合金のヤング率を示す。図９を参照し、いずれの試料もＭｏおよびＭｏ－Ｓｉ合金に比べ室温から１０００℃までにおいてヤング率が大きい。このように、試料Ａ３およびＢ３は、高温において剛性が高いことがわかる。 FIG. 9 is a diagram showing the measurement results of Young's modulus with respect to the temperatures of samples A3 and B3. For comparison, the Young's modulus of W (tungsten), Mo, Mo-2Si alloy and Mo-3Si alloy is shown. Referring to FIG. 9, each sample has a higher Young's modulus from room temperature to 1000 ° C. than Mo and Mo—Si alloy. Thus, it can be seen that Samples A3 and B3 have high rigidity at high temperatures.
　図１０は、試料Ａ１～Ａ４およびＢ１～Ｂ４の密度を示す図である。比較のため純Ｎｉ（ニッケル）、Ｒｅｎｅ´Ｎ５合金、ＴＭＳ－１３８合金、Ｍｏ５ＳｉＢ２および純Ｍｏの密度を示す。図６を参照し、試料Ａ１～Ａ４およびＢ１～Ｂ４の密度は８．７ｇ／ｃｍ３から９．０１ｇ／ｃｍ３である。試料Ａ１～Ａ４およびＢ１～Ｂ４は、純Ｍｏより密度が小さく、Ｎｉ合金であるＲｅｎｅ´Ｎ５合金およびＴＭＳ－１３８合金並びにＭｏ５ＳｉＢ２と同程度の密度である。 FIG. 10 is a diagram showing the densities of samples A1 to A4 and B1 to B4. For comparison, the densities of pure Ni (nickel), Rene′N5 alloy, TMS-138 alloy, Mo 5 SiB 2 and pure Mo are shown. Referring to FIG. 6, the density of samples A1 to A4 and B1 to B4 is 8.7 g / cm 3 to 9.01 g / cm 3 . Samples A1 to A4 and B1 to B4 have a density lower than that of pure Mo, and the same density as that of Ni 'alloys Rene′N5 alloy, TMS-138 alloy, and Mo 5 SiB 2 .
　純Ｎｉ、ＲｅｎｅＮ５合金およびＴＭＳ－１３８合金は、密度が小さく軽量であるが融点が１４００℃程度であり、１５００℃程度で用いられる高耐熱合金として用いることができない。Ｍｏ５ＳｉＢ２は軽量であり高耐熱であるが、融点が２２００℃程度であり、鋳造法による製造が難しい。 Pure Ni, ReneN5 alloy and TMS-138 alloy are small in density and lightweight, but have a melting point of about 1400 ° C. and cannot be used as a high heat-resistant alloy used at about 1500 ° C. Mo 5 SiB 2 is lightweight and highly heat resistant, but has a melting point of about 2200 ° C. and is difficult to manufacture by a casting method.
　実施例に係る合金は、Ｍｏ、Ｓｉ、Ｂ、ＴｉおよびＣを主成分とする。これにより、表３に示すように、２０００℃程度で溶解可能であり、鋳造法を用い合金を製造が可能である。図６から図９に示すように、１０００℃以上の高温において高強度かつ高剛性である。さらに、図１０に示すように、軽量である。 The alloys according to the examples are mainly composed of Mo, Si, B, Ti and C. Thereby, as shown in Table 3, it can melt | dissolve at about 2000 degreeC and can manufacture an alloy using a casting method. As shown in FIGS. 6 to 9, it has high strength and high rigidity at a high temperature of 1000 ° C. or higher. Furthermore, as shown in FIG.
　Ｍｏの組成比は５２原子％以上かつ８０原子％以下であり、Ｓｉの組成比は１．５原子％以上かつ２５原子％以下であり、Ｂの組成比は３原子％以上かつ２５原子％以下であり、Ｔｉの組成比は０．１原子％以上かつ１５原子％以下であり、Ｃの組成比は、０．１原子％以上かつ１５原子％以下であることが好ましい。これにより、低温での溶解が可能となる。 The composition ratio of Mo is 52 atomic% or more and 80 atomic% or less, the composition ratio of Si is 1.5 atomic% or more and 25 atomic% or less, and the composition ratio of B is 3 atomic% or more and 25 atomic% or less. The composition ratio of Ti is preferably 0.1 atomic% or more and 15 atomic% or less, and the composition ratio of C is preferably 0.1 atomic% or more and 15 atomic% or less. Thereby, dissolution at a low temperature becomes possible.
　Ｍｏ－Ｓｉ－Ｂ三元系の融点の知見から、低融点化のため、Ｍｏの組成比は８０原子％以下が好ましい。高強度化のため、Ｍｏの組成比は５２原子％以上が好ましい。Ｍｏ－Ｓｉ－Ｂ三元系をベースとするため、Ｓｉの組成比は１．５原子％以上かつ２５原子％以下であり、Ｂの組成比は３原子％以上かつ２５原子％以下であることが好ましい。ＴｉおよびＣは、低融点化のため、０．１原子％以上が好ましい。 From the knowledge of the melting point of the Mo—Si—B ternary system, the Mo composition ratio is preferably 80 atomic% or less in order to lower the melting point. In order to increase the strength, the Mo composition ratio is preferably 52 atomic% or more. Since it is based on the Mo—Si—B ternary system, the composition ratio of Si is 1.5 atomic% or more and 25 atomic% or less, and the composition ratio of B is 3 atomic% or more and 25 atomic% or less. Is preferred. Ti and C are preferably 0.1 atomic percent or more for lowering the melting point.
　図２（ａ）から図５（ｂ）に示すように、これらの合金は、Ｍｏ固溶体相、Ｍｏ２Ｃ、Ｍｏ５ＳｉＢ２およびＴｉＣの共相であることにより、融点が低く、高強度かつ軽量化を実現できる。 As shown in FIG. 2 (a) to FIG. 5 (b), these alloys have a low melting point, high strength and high strength due to the co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and TiC. Light weight can be realized.
　表３のように、Ｍｏ、ＳｉおよびＢを主成分とする比較例においては、溶解温度を２１００℃以下とするため、Ｍｏの組成比が６５原子％以上であり、かつＢの組成比が２０原子％以下であることが好ましい。また、Ｍｏの組成比は、７５原子％以下が好ましい。Ｂの組成比は１０原子％以上が好ましい。溶解温度を２０００℃以下とするため、Ｍｏの組成比が６７原子％以上であり、かつＢの組成比が１５原子％以下であることが好ましい。Ｍｏの組成比は、７３原子％以下が好ましい。Ｂの組成比は１０原子％以上が好ましい。しかしながら、比較例においては、密度が９．１ｇ／ｃｍ３以上となってしまう。よって、合金の軽量化が難しい。Ｍｏの組成比を６２．５原子％、Ｂの組成比を２５原子％およびＳｉの組成比を１２．５原子％とすると、合金の密度を約８．８ｇ／ｃｍ３とすることができる。しかしながら、溶解温度が高くなる。実施例では、密度をほぼ９．０ｇ／ｃｍ３以下とすることができ、かつ溶解温度を低くすることができる。よって、比較的低温において溶解可能であり、かつ合金の軽量化が容易である。 As shown in Table 3, in the comparative example mainly composed of Mo, Si and B, the melting temperature is set to 2100 ° C. or lower, so that the Mo composition ratio is 65 atomic% or more and the B composition ratio is 20 It is preferably at most atomic%. Further, the Mo composition ratio is preferably 75 atomic% or less. The composition ratio of B is preferably 10 atomic% or more. In order to set the melting temperature to 2000 ° C. or less, it is preferable that the Mo composition ratio is 67 atomic% or more and the B composition ratio is 15 atomic% or less. The composition ratio of Mo is preferably 73 atomic percent or less. The composition ratio of B is preferably 10 atomic% or more. However, in the comparative example, the density is 9.1 g / cm 3 or more. Therefore, it is difficult to reduce the weight of the alloy. When the Mo composition ratio is 62.5 atomic%, the B composition ratio is 25 atomic%, and the Si composition ratio is 12.5 atomic%, the density of the alloy can be about 8.8 g / cm 3 . However, the melting temperature increases. In the examples, the density can be reduced to about 9.0 g / cm 3 or less, and the melting temperature can be lowered. Therefore, it can be melted at a relatively low temperature and the alloy can be easily reduced in weight.
　ＺｒおよびＨｆは、周期律表においてＴｉと同じ周期であり、性質がＴｉと似ている。例えば、ＣまたはＮとの親和力が大きい。よって、Ｔｉの代わりにＺｒおよびＨｆを用いることができる。軽量化のためには、Ｔｉが好ましい。また、合金化した際にＮはＣと同様な挙動を示すため、Ｃの代わりにＮを用いることもできる。よって、合金は、Ｍｏと、Ｓｉと、Ｂと、Ｔｉと、ＺｒおよびＨｆの少なくとも１つの元素と、ＣおよびＮの少なくとも１つの元素と、を主成分とすればよい。 Zr and Hf have the same period as Ti in the periodic table, and the properties are similar to Ti. For example, the affinity with C or N is large. Therefore, Zr and Hf can be used instead of Ti. Ti is preferable for weight reduction. Moreover, since N shows the same behavior as C when alloyed, N can be used instead of C. Therefore, the alloy may be composed mainly of Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N.
　例えば、Ｍｏ：Ｓｉ：Ｂ：Ｔｉ：Ｃ：Ｚｒ＝５２：８：１０：１０：１０（原子比）の試料を作製した。この試料の密度は約８．１ｇ／ｃｍ３であり、２０００℃において溶解した。 For example, a sample of Mo: Si: B: Ti: C: Zr = 52: 8: 10: 10: 10 (atomic ratio) was prepared. The density of this sample was about 8.1 g / cm 3 and dissolved at 2000 ° C.
　合金は、Ｍｏ、Ｓｉ、Ｂ、ＺｒおよびＣを主成分とすることができる。また、合金は、Ｍｏ、Ｓｉ、Ｂ、Ｔｉ、ＺｒおよびＣを主成分とすることができる。この場合、合金は、Ｍｏ固溶体相、Ｍｏ２Ｃ、Ｍｏ５ＳｉＢ２およびＺｒＣの共相であることにより、融点が低く、高強度かつ軽量化を実現できる。 The alloy can be mainly composed of Mo, Si, B, Zr and C. Further, the alloy can contain Mo, Si, B, Ti, Zr and C as main components. In this case, since the alloy is a co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and ZrC, the melting point is low, and high strength and light weight can be realized.
　図１のステップＳ１０における材料としては、Ｍｏ、Ｓｉ、Ｂ、ＴｉＣ、ＴｉＮ、ＴｉおよびＺｒ等を適宜用いることができる。ステップＳ１２における材料の溶解方法としては、アーク溶解法以外にもプラズマ溶解法等を用いることができる。 As the material in step S10 in FIG. 1, Mo, Si, B, TiC, TiN, Ti, Zr, or the like can be used as appropriate. As a material melting method in step S12, a plasma melting method or the like can be used in addition to the arc melting method.
　Ｍｏと、Ｓｉと、Ｂと、Ｔｉと、ＺｒおよびＨｆの少なくとも１つの元素と、ＣおよびＮの少なくとも１つの元素と、を主成分とする合金は、２０００℃程度の温度で溶解するため、安価な設備を用い製造することができる。また、複雑な形状の製品および／または大型な製品を簡単に製造することができる。また、１０００℃以上の温度において強度を高くでき、軽量化が可能である。このため、この合金は、耐熱合金として、ジェットエンジンやガスタービンの高圧タービンブレードに適用可能となる。また、ＷＣ（炭化タングステン）に代わり各種加工ツールや特殊金型にも応用することができる。さらに、高温高圧容器に使用することもできる。 An alloy mainly composed of Mo, Si, B, Ti, at least one element of Zr and Hf, and at least one element of C and N is dissolved at a temperature of about 2000 ° C. It can be manufactured using inexpensive equipment. Further, a product having a complicated shape and / or a large product can be easily manufactured. Further, the strength can be increased at a temperature of 1000 ° C. or higher, and the weight can be reduced. For this reason, this alloy can be applied to a high-pressure turbine blade of a jet engine or a gas turbine as a heat-resistant alloy. Moreover, it can be applied to various processing tools and special molds in place of WC (tungsten carbide). Furthermore, it can be used for a high-temperature and high-pressure vessel.
　以上、発明の好ましい実施例について詳述したが、本発明は係る特定の実施例に限定されるものではなく、特許請求の範囲に記載された本発明の要旨の範囲内において、種々の変形・変更が可能である。 The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific embodiments, and various modifications and changes can be made within the scope of the gist of the present invention described in the claims. It can be changed.

Claims (12)

  1. 　Ｍｏと、Ｓｉと、Ｂと、Ｔｉ、ＺｒおよびＨｆの少なくとも１つの元素と、ＣおよびＮの少なくとも１つの元素と、を主成分とすることを特徴とする合金。 An alloy comprising Mo, Si, B, at least one element of Ti, Zr and Hf, and at least one element of C and N as main components.
  2. 　鋳造されたことを特徴とする請求項１記載の合金。 The alloy according to claim 1, wherein the alloy is cast.
  3. 　前記Ｔｉ、ＺｒおよびＨｆの少なくとも１つの元素はＴｉであり、前記ＣおよびＮの少なくとも１つの元素はＣであることを特徴とする請求項１または２記載の合金。 3. The alloy according to claim 1 or 2, wherein at least one element of Ti, Zr and Hf is Ti, and at least one element of C and N is C.
  4. 　Ｍｏ固溶体相、Ｍｏ２Ｃ、Ｍｏ５ＳｉＢ２およびＴｉＣの共相であることを特徴とする請求項３記載の合金。 The alloy according to claim 3, wherein the alloy is a co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and TiC.
  5. 　Ｍｏの組成比は５２原子％以上かつ８０原子％以下であり、Ｓｉの組成比は１．５原子％以上かつ２５原子％以下であり、Ｂの組成比は３原子％以上かつ２５原子％以下であり、Ｔｉの組成比は０．１原子％以上かつ１５原子％以下であり、Ｃの組成比は、０．１原子％以上かつ１５原子％以下であることを特徴とする請求項３記載の合金。 The composition ratio of Mo is 52 atomic% or more and 80 atomic% or less, the composition ratio of Si is 1.5 atomic% or more and 25 atomic% or less, and the composition ratio of B is 3 atomic% or more and 25 atomic% or less. The composition ratio of Ti is 0.1 atomic% or more and 15 atomic% or less, and the composition ratio of C is 0.1 atomic% or more and 15 atomic% or less. Alloy.
  6. 　Ｍｏの組成比は６０原子％以上かつ７５原子％以下であり、Ｓｉの組成比は１．７原子％以上かつ６．７原子％以下であり、Ｂの組成比は３．３原子％以上かつ１３．３原子％以下であり、Ｔｉの組成比は５．０原子％以上かつ１５．０原子％以下であり、Ｃの組成比は、５．０原子％以上かつ１５．０原子％以下であることを特徴とする請求項３記載の合金。 The composition ratio of Mo is 60 atomic% or more and 75 atomic% or less, the composition ratio of Si is 1.7 atomic% or more and 6.7 atomic% or less, and the composition ratio of B is 3.3 atomic% or more and The composition ratio of Ti is 5.0 atomic% or more and 15.0 atomic% or less, and the composition ratio of C is 5.0 atomic% or more and 15.0 atomic% or less. 4. An alloy according to claim 3, characterized in that it is present.
  7. 　Ｔｉの組成比は１０原子％以上であり、かつＣの組成比は１０原子％以下であることを特徴とする請求項６記載の合金。 The composition ratio of Ti is 10 atomic% or more, and the composition ratio of C is 10 atomic% or less.
  8. 　前記Ｔｉ、ＺｒおよびＨｆの少なくとも１つの元素はＺｒであり、前記ＣおよびＮの少なくとも１つの元素はＣであることを特徴とする請求項１または２記載の合金。 3. The alloy according to claim 1, wherein at least one element of Ti, Zr and Hf is Zr, and at least one element of C and N is C.
  9. 　Ｍｏ固溶体相、Ｍｏ２Ｃ、Ｍｏ５ＳｉＢ２およびＺｒＣの共相であることを特徴とする請求項８記載の合金。 The alloy according to claim 8, which is a co-phase of Mo solid solution phase, Mo 2 C, Mo 5 SiB 2 and ZrC.
  10. 　Ｍｏと、Ｓｉと、Ｂと、Ｔｉ、ＺｒおよびＨｆの少なくとも１つの元素と、ＣおよびＮの少なくとも１つの元素と、を主成分とする合金を鋳造法を用い製造することを特徴とする合金の製造方法。 An alloy characterized by producing an alloy containing Mo, Si, B, at least one element of Ti, Zr, and Hf and at least one element of C and N using a casting method. Manufacturing method.
  11. 　前記Ｔｉ、ＺｒおよびＨｆの少なくとも１つの元素はＴｉであり、前記ＣおよびＮの少なくとも１つの元素はＣであることを特徴とする請求項１０記載の合金の製造方法。 The method for producing an alloy according to claim 10, wherein at least one element of Ti, Zr, and Hf is Ti, and at least one element of C and N is C.
  12. 　前記Ｔｉ、ＺｒおよびＨｆの少なくとも１つの元素はＺｒであり、前記ＣおよびＮの少なくとも１つの元素はＣであることを特徴とする請求項１０記載の合金の製造方法。
    　     The method for producing an alloy according to claim 10, wherein at least one element of Ti, Zr, and Hf is Zr, and at least one element of C and N is C.
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